Durable, High Performance Wire Grid Polarizer

ABSTRACT

A method for making a wire grid polarizer (WGP) can provide WGPs with high temperature resistance, robust wires, oxidation resistance, and corrosion protection. In one embodiment, the method can comprise: (a) providing an array of wires on a bottom protection layer; (b) applying a top protection layer on the wires, spanning channels between wires; then (c) applying an upper barrier-layer on the top protection layer and into the channels through permeable junctions in the top protection layer. In a variation of this embodiment, the method can further comprise applying a lower barrier-layer before applying the top protection layer. In another variation, the bottom protection layer and the top protection layer can include aluminum oxide. In another embodiment, the method can comprise applying on the WGP an amino phosphonate then a hydrophobic chemical.

CLAIM OF PRIORITY

This application is a continuation of U.S. patent application Ser. No.16/150,478, filed Oct. 3, 2018; which is a continuation-in-part of U.S.patent application Ser. No. 15/709,127, filed on Sep. 19, 2017; U.S.patent application Ser. No. 15/691,315, filed on Aug. 30, 2017, whichclaims priority to U.S. Provisional Patent Application No. 62/425,339,filed on Nov. 22, 2016; and U.S. patent application Ser. No. 15/631,256,filed on Jun. 23, 2017, which claims priority to US Provisional PatentApplication No. 62/375,675, filed on Aug. 16, 2016, all of which areincorporated herein by reference.

FIELD OF THE INVENTION

The present application is related generally to wire gird polarizers.

BACKGROUND

Demand for improved wire grid polarizer (WGP) durability is increasing.For example, a WGP may need to withstand high temperatures, such as forexample in newer computer projectors which are progressively becomingsmaller and brighter with accompanying higher internal temperature.

Selectively-absorptive WGPs are particularly susceptible to damage dueto high temperature because they absorb a large percent of incidentlight. Such WGPs typically have wires that include a reflective portion(e.g. aluminum) and an absorptive portion (e.g. silicon). The absorptiveportion can absorb about 80%-90% of one polarization of light, and thusover 40% of the total amount of light. Much of the heat from thisabsorbed light conducts to the reflective portion of the wire, which canmelt, thus destroying the WGP.

The wires in a visible light WGP can be narrow (about 30 nm) and tall(about 300 nm) and consequently delicate. It is difficult to protectthese wires from toppling without degradation of WGP performance.

Oxidation of wires of a WGP can degrade or destroy WGP performance. Aswith protection from toppling, it is difficult to protect wires fromoxidation without the protective mechanism degrading WGP performance.

It is also important to protect wires of the WGP from corrosion. Due tothe nanometer-size of the wires, and high performance requirements, evena small amount of corrosion can make the WGP unsatisfactory. It isdifficult to provide sufficient corrosion protection without causingperformance to drop below minimum standards.

SUMMARY

It has been recognized that it would be advantageous to protect a wiregrid polarizer (WGP) from high temperature damage, wire toppling,oxidation, and corrosion. The present invention is directed to variousmethods of manufacturing WGPs that satisfy these needs. Each embodimentmay satisfy one, some, or all of these needs.

In one embodiment, the method can comprise: (a) providing an array ofwires on a bottom protection layer; (b) applying a top protection layeron the wires, spanning channels between wires; then (c) applying anupper barrier-layer on the top protection layer and into the channelsthrough permeable junctions in the top protection layer. In a variationof this embodiment, the method can further comprise applying a lowerbarrier-layer before applying the top protection layer. In anothervariation, the bottom protection layer and the top protection layer caninclude aluminum oxide.

In another embodiment, the method can comprise applying an aminophosphonate then a hydrophobic chemical, both as conformal coatings, onthe wires.

BRIEF DESCRIPTION OF THE DRAWINGS (DRAWINGS MIGHT NOT BE DRAWN TO SCALE)

FIG. 1 is a schematic, cross-sectional side-view of a wire gridpolarizer (WGP) 10, comprising an array of wires 12 (length extendinginto the page) sandwiched between a pair of protection layers 14,including a top protection layer 14 _(U) and a bottom protection layer14 _(L), in accordance with an embodiment of the present invention.

FIG. 2 is a schematic, cross-sectional side-view of a WGP 20, similar toWGP 10, further comprising each channel 13 extending beyond a proximalend 12 _(p) of the wires 12 into the bottom protection layer 14 _(L) andbeyond a distal end 12 _(d) of the wires 12 into the top protectionlayer 14 _(U), in accordance with an embodiment of the presentinvention.

FIG. 3 is a schematic, cross-sectional side-view of a WGP 30, similar tothe WGPs of FIGS. 1-2, further comprising a lower barrier-layer 31 at aside-wall surface 12 _(s) of the wires 12 in the channels 13, a surface1411 of the bottom protection layer 14 _(L) in the channels 13, andbetween the distal end 12 _(d) each wire 12 and the top protection layer14 _(U), in accordance with an embodiment of the present invention.

FIG. 4 is a schematic, cross-sectional side-view of a WGP 40, similar tothe WGPs of FIGS. 1-2, further comprising an upper barrier-layer 41located at an outermost surface 14 _(UO) of the top protection layer 14_(U), at an outermost surface 14 _(LO) of the bottom protection layer 14_(L), at surfaces of the channels 13, or combinations thereof, inaccordance with an embodiment of the present invention.

FIG. 5 is a schematic, cross-sectional side-view of a WGP 50, with alower barrier-layer 31 (see FIG. 3) and an upper barrier-layer 41 (seeFIG. 4), in accordance with an embodiment of the present invention.

FIG. 6 is a schematic, cross-sectional side-view of a WGP 60, similar tothe WGPs of FIGS. 1-5, further comprising each of the wires 12 includinga reflective layer 62 sandwiched between absorptive layers 63, inaccordance with an embodiment of the present invention.

FIG. 7 is a schematic, cross-sectional side-view of WGP 70, comprisingan array of wires 12 on a protection layer 14, and an upperbarrier-layer 41 on the wires 12 and on the protection layer 14, inaccordance with an embodiment of the present invention.

FIG. 8 is a schematic, cross-sectional side-view of WGP 80, comprisingan array of wires 12 sandwiched between a top protection layer 14 _(U)and a substrate 61, in accordance with an embodiment of the presentinvention.

FIG. 9 is a schematic, cross-sectional side-view of an optical system90, comprising at least one WGP 94 according to a design describedherein, in accordance with an embodiment of the present invention.

FIG. 10 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including applying film(s) 102 on top of thebottom protection layer 14 _(L), in accordance with an embodiment of thepresent invention.

FIG. 11 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including etching the film(s) 102 to form anarray of wires 12 and channels 13 between adjacent wires 12, inaccordance with an embodiment of the present invention.

FIG. 12 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including etching beyond the proximal end 12_(p) of the wires 12 into the bottom protection layer 14 _(L) for adepth D_(14L), thus increasing the size of the channels 13, inaccordance with an embodiment of the present invention.

FIG. 13 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including applying a lower barrier-layer 31 toan exposed surface of the wires 12 and a surface 14 _(LI) of the bottomprotection layer 14 _(L) in the channels 13, or both, in accordance withan embodiment of the present invention.

FIG. 14 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including applying a top protection layer 14_(U) at a distal end 12 _(d) of the wires and spanning the channels 13,in accordance with an embodiment of the present invention.

FIG. 15 is a schematic, cross-sectional side-view illustrating a step ina method of making a WGP, including applying an upper barrier-layer 41at an outermost surface 14 _(UO) of the top protection layer 14 _(U), atan outermost surface 14 _(LO) of the bottom protection layer 14 _(L), atsome or all surfaces of the channels 13, or combinations thereof, inaccordance with an embodiment of the present invention.

DEFINITIONS

As used herein, the term “adjoin” means direct and immediate contact. Asused herein, the terms “adjacent” and “located at” include adjoin, butalso include near or next to with other solid material(s) between.

As used herein, the term “conformal coating” means a thin film whichconforms to the contours of feature topology. For example, “conformal”can mean that a minimum thickness of the coating is ≥0.1 nm or ≥1 nm anda maximum thickness of the coating is ≥10 nm, ≤25 nm, or ≤40 nm. Asanother example, “conformal” can mean that a maximum thickness dividedby a minimum thickness of the coating is ≤20, ≤10, ≤5, or ≤3.

As used herein “continuous” means a layer which may include somediscontinuity, such as pinholes, but no major discontinuity, such as adivision into a grid or separate wires.

As used herein, the term “equal” with regard to thicknesses meansexactly equal, equal within normal manufacturing tolerances, or nearlyequal, such that any deviation from exactly equal would have negligibleeffect for ordinary use of the device.

As used herein, the term “nm” means nanometer(s), the term μm meansmicrometer(s), and the term “mm” means millimeter(s).

As used herein, the term “parallel” means exactly parallel, parallelwithin normal manufacturing tolerances, or nearly parallel, such thatany deviation from exactly parallel would have negligible effect forordinary use of the device.

The terms “upper”, “lower”, “top”, and “bottom” are for convenience inreferring to the drawings and for distinguishing different WGPcomponents, but the WGP may be spatially arranged in any configuration.

Materials used in optical structures can absorb some light, reflect somelight, and transmit some light. The following definitions distinguishbetween materials that are primarily absorptive, primarily reflective,or primarily transparent. Each material can be considered to beabsorptive, reflective, or transparent in a specific wavelength range(e.g. ultraviolet, visible, or infrared spectrum) and can have adifferent property in a different wavelength range.

Thus, whether a material is absorptive, reflective, or transparent isdependent on the intended wavelength range of use. Materials are dividedinto absorptive, reflective, and transparent based on reflectance R, thereal part of the refractive index n, and the imaginary part of therefractive index/extinction coefficient k. Equation 1 is used todetermine the reflectance R of the interface between air and a uniformslab of the material at normal incidence:

$\begin{matrix}{R = \frac{\left( {n - 1} \right)^{2} + k^{2}}{\left( {n + 1} \right)^{2} + k^{2}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

Unless explicitly specified otherwise herein, materials with k≤0.1 inthe specified wavelength range are “transparent” materials, materialswith k≥0.1 and R≤0.6 in the specified wavelength range are “absorptive”materials, and materials with k≥0.1 and R≥0.6 in the specifiedwavelength range are “reflective” materials. If not explicitly specifiedin the claims, then the material is presumed to have the property oftransparent, absorptive, or reflective across the visible wavelengthrange.

DETAILED DESCRIPTION

As illustrated in FIGS. 1-8, each wire grid polarizer (WGP) can includean array of wires 12. The wires 12 can be made of or can includematerials for polarization of light, including metals and/ordielectrics, as are typically used in wires of wire grid polarizers. Seefor example U.S. Pat. Nos. 7,961,393 and 8,755,113, which areincorporated herein by reference.

As illustrated in FIGS. 1-6, the array of wires 12 can be sandwichedbetween a pair of protection layers 14, including a top protection layer14 _(U) and a bottom protection layer 14 _(L). The protection layers 14can have a flat, planar shape.

The protection layers 14 can provide the following benefits: increasedresistance to high temperature, protection of the wires 12 fromtoppling, protection of the wires against oxidation, protection of thewires against corrosion, or combinations thereof. As described in thevarious embodiments herein, this protection may be achieved with littleor no degradation of WGP performance.

The protection layers 14 can have a high coefficient of thermalconductivity to conduct heat away from the wires 12. For example, one orboth of the protection layers 14 can have a coefficient of thermalconductivity of ≥2 W/(m*K), ≥2.5 W/(m*K), ≥4 W/(m*K), ≥5 W/(m*K), ≥10W/(m*K), ≥15 W/(m*K), ≥20 W/(m*K), or ≥25 W/(m*K). All coefficient ofthermal conductivity values specified herein are the value at 25° C.

The protection layers 14 can have a high melting temperature to improveheat resistance. For example, one or both of the protection layers 14can have a melting temperature of ≥600° C., ≥1000° C., ≥1500° C., or≥1900° C.

The protection layers 14 can have a high Young's modulus in order toprovide structural support for the wires 12. For example, the materialof one or both of the protection layers 14 can have a Young's modulus of≥1 GPa, ≥10 GPa, ≥30 GPa, ≥100 GPa, or ≥200 GPa.

The protection layers 14 can extend at least partially along theside-wall surfaces 125 of the wires 12 in the channels 13; therefore,these protection layers 14 can provide protection to these side-wallsurfaces 12 _(s). Thus, it can be important for the protection layers 14to have a low oxygen diffusion coefficient and thus provide addedoxidation protection for the wires 12. It can thus be beneficial if theoxygen diffusion coefficient of the protection layers 14 is ≥10⁻²⁰ m²/s,≤10⁻²¹ m²/s, ≤10⁻²² m²/s, ≤10⁻²³ m²/s, or ≤10⁻²⁴ m²/s, all measured at325° C.

Corrosion from condensed water is a common failure mechanism for WGPs.It can therefore be helpful for the protection layers 14 to be insolublein water. Thus, for example, water solubility of the protection layers14 can be ≤1 g/L, ≤0.1 g/L, ≤0.01 g/L, or ≤0.005 g/L, ≤0.001 g/L, allmeasured at 25° C.

It can be important for the protection layers 14 to have minimal adverseeffect, or even improve, performance of the WGP. Optimal refractiveindex n and extinction coefficient k can vary depending on overall WGPdesign. Following are exemplary values of the refractive index n and theextinction coefficient k for the protection layers 14 across theinfrared, visible light, or ultraviolet spectrum of light: n≥1.1 orn≥1.3; n≤1.8, n≤2.0, n≤2.2, or n≤2.5; and k≤0.1, k≤0.06, or k≤0.03.

The protection layer 14 can have high electrical resistivity. Forexample, the protection layer 14 can have electrical resistivity of ≥10⁴Ω*cm, ≥10⁵ Ω*cm, ≥10⁶ Ω*cm, ≥10⁷ Ω*cm, ≥10⁸ Ω*cm, ≥10⁹ Ω*cm, or 10¹⁰Ω*cm. Some materials can function well as the protection layer 14without such a high electrical resistivity. For example, the protectionlayer 14 can have electrical resistivity of ≥0.0001 Ω*cm or ≥0.0005 Ω*cmand ≤1 Ω*cm or ≤100 Ω*cm. The electrical resistivity values specifiedherein are the electrical resistivity at 20° C.

Example materials for the protection layer(s) 14, which meet at leastsome of the above criteria, include zinc oxide, silicon dioxide,aluminum-doped zinc oxide, aluminum nitride, and aluminum oxide. Forexample, one protection layer 14 or both protection layers 14 cancomprise ≥50%, ≥75%, ≥90%, ≥95%, or ≥99% zinc oxide, silicon dioxide,aluminum-doped zinc oxide, aluminum nitride, or aluminum oxide. Due toimperfections in deposition of material, these materials can bedeposited in nonstoichiometric ratios. Therefore, the term aluminumoxide (Al₂O₃) used herein means approximately two aluminum atoms forevery three oxygen atoms, such as for example Al_(x)O_(y), where1.9≤x≤2.1 and 2.95≤y≤3.1. The term aluminum nitride (AlN) used hereinmeans approximately one aluminum atom for every one nitrogen atom, suchas for example Al_(m)N_(n), where 0.9≤m≤1.1 and 0.9≤n≤1.1. The term zincoxide (ZnO) used herein means approximately one zinc atom for every oneoxygen atom, such as for example Zn_(i)O_(j), where 0.95≤i≤1.1 and0.9≤j≤1.1.

Selection of a thickness Th_(14U) of the top protection layer 14 _(U)and a thickness Th_(14L) of the bottom protection layer 14 _(L) canimprove the ability of these protection layers 14 to provide the neededprotection to the WGP with reduced detrimental effect to WGPperformance, improved manufacturability, and reduced cost. Thesethicknesses Th_(14U) and Th_(14L) can vary depending on specificapplication.

In some applications, for WGP symmetry, the thickness Th_(14U) of thetop protection layer 14 _(U) can equal, or be very close to, thethickness of the Th_(14L) bottom protection layer 14 _(L). This designcan be beneficial for interferometry and 3D projection displays asdescribed more fully in U.S. Pat. No. 9,726,897. For example,|Th_(14L)−Th_(14U)|≤1 nm, |Th_(14L)−Th_(14U)|≤10 nm, or|Th_(14L)−Th_(14U)|≤100 nm.

In other applications, particularly for applications requiring minimalor no projected image distortion, it can be beneficial for the thicknessTh_(14U) of the top protection layer 14 _(U) to be substantiallydifferent from the thickness of the Th_(14L) bottom protection layer 14_(L). For example, Th_(14L)/Th_(14U)≥10, Th_(14L)/Th_(14U)≥100,Th_(14L)/Th_(14U)≥1000, or Th_(14L)/Th_(14U)≥2000; andTh_(14L)/Th_(14U)≤10,000 or Th_(14L)/Th_(14U)≤100,000.

Examples of the thickness Th_(14U) of the top protection layer 14 _(U)include ≥10 nm, ≥100 nm, ≥1 μm, ≥10 μm, ≥100 μm, ≥300 μm, or ≥600 μm;and ≤300 nm, ≤1 μm, ≤1 mm, or ≤5 mm. Examples of the thickness Th_(14L)of the bottom protection layer 14 _(L) include ≥10 nm, ≥100 nm, ≥1 μm,≥10 μm, ≥100 μm, ≥300 μm, or ≥600 μm; and ≥300 nm, ≤1 μm, ≤1 mm, or ≤5mm.

Each wire 12 of the array can include a proximal end 12 _(p) closest tothe bottom protection layer 14 _(L) and a distal end closest to the topprotection layer 14 _(U). The array of wires 12 can be parallel. Thewires 12 can also be elongated. As used herein, the term “elongated”means that a length of the wires 12 is substantially greater than wirewidth W₁₂ or wire thickness Th₁₂ (see WGP 10 in FIG. 1). The wire lengthis the dimension extending into the page of the figures. For example,the wire length can be ≥10 times, ≥100 times, ≥1000 times, or ≥10,000times larger than wire width W₁₂, wire thickness Th₁₂, or both.

Channels

The array of wires 12 can include alternating wires 12 and channels 13,with a channel 13 between each pair of adjacent wires 12. The protectionlayers 14 can span the channels 13 and either not extend into thechannels 13 or extend only minimally into the channels 13. Thus, thechannels 13 can be air-filled for improved WGP performance.

The size of the channels 13 can be increased for improved WGPperformance. As illustrated on WGP 20 in FIG. 2, each channel 13 canextend beyond the proximal end 12 _(p) of the wires 12 into the bottomprotection layer 14 _(L) for a depth D_(14L), beyond the distal end 12_(d) of the wires 12 into the top protection layer 14 _(U) for a depthD_(14U), or both. Each of these extensions of the channels 13 into theprotection layers 14, to increase the size of the channels, can improveWGP performance due to an increased volume of low-index air in thechannels 13.

A value for each of these depths D_(14L) and D_(14U), and a relationshipbetween these depths D_(14L) and D_(14U), can vary depending on theapplication. Following are some examples such values and relationshipswhich have proven effective in certain designs: D_(14L)≥1 nm, D_(14L)≥5nm, D_(14L)≥10 nm, D_(14L)≥30 nm; D_(14L)≤50 nm, D_(14L)≤100 nm,D_(14L)≤200 nm, D_(14L)≤500 nm; D_(14U)≥1 nm, D_(14U)≥5 nm, D_(14U)≥10nm, D_(14U)≥30 nm; D_(14U)≤50 nm, D_(14U)≤100 nm, D_(14U)≤200 nm,D_(14U)≤500 nm; |D_(14L)−D_(14U)|≥1 nm; and |D_(14L)−D_(14U)|≤5 nm,|D_(14L)−D_(14U)|≤10 nm, |D_(14L)−D_(14U)|≤20 nm, |D_(14L)−D_(14U)|≤30nm, |D_(14L)−D_(14U)|≤50 nm, or |D_(14L)−D_(14U)|≤200 nm. These depthsD_(14L) and D_(14U) are measured in a direction parallel to thethickness T₁₂ of the wires 12. A method for increasing the size of thechannels 13 is described below in the method of making section.

Lower Barrier-Layer

As illustrated on WGP 30 in FIG. 3, a lower barrier-layer 31 can belocated between the distal end 12 _(d) of each wire 12 and the topprotection layer 14 _(U), a side-wall surface 12 _(s) of the wires 12 inthe channels 13, a surface 14 _(LI) of the bottom protection layer 14_(L) in the channels 13, or combinations thereof. The lowerbarrier-layer 31 can be a conformal coating. The lower barrier-layer 31can cover a large percent of the covered regions, such as for example≥50%, ≥75%, ≥90%, ≥95%, or ≥99%. The amount of coverage can depend ontool used for application and thickness T₃₁ of the lower barrier-layer31.

The lower barrier-layer 31 can be absent or not located between eachwire 12 and the bottom protection layer 14 _(L), which can improveadhesion of the wires 12 to the bottom protection layer 14 _(L) andreduce chemical cost. Thus, the proximal end 12 _(p) of each wire 12 canadjoin the bottom protection layer 14 _(L). Furthermore, the lowerbarrier-layer 31 can be absent or not located at an outermost surface 14_(UO) of the top protection layer 14 _(UI) an outermost surface 14 _(LO)of the bottom protection layer 14 _(L), or both. The lower barrier-layer31 can be absent or not located at an innermost surface 14 _(UI) of thetop protection layer 14 _(U) adjacent and facing the channels 13, whichcan improve adhesion of the upper barrier-layer 41 (described below) tothe top protection layer 14 _(U).

The lower barrier-layer 31 can include various chemicals to protectagainst oxidation, corrosion, or both. For example, the lowerbarrier-layer 31 can include aluminum oxide, silicon oxide, siliconnitride, silicon oxynitride, silicon carbide, hafnium oxide, zirconiumoxide, a rare earth oxide, or combinations thereof. The lowerbarrier-layer 31 can include other metal oxides or layers of differentmetal oxides.

In one embodiment, for both oxidation protection and corrosionprotection, the lower barrier-layer 31 can comprise two layers ofdifferent materials, including an oxidation-barrier and amoisture-barrier. The oxidation-barrier can be located between themoisture-barrier and the wires. The oxidation-barrier can be distinctfrom the wires and can include aluminum oxide, silicon oxide, siliconnitride, silicon oxynitride, silicon carbide, a rare earth oxide, orcombinations thereof. The moisture-barrier can include hafnium oxide,zirconium oxide, a rare earth oxide different from the rare earth oxideof the oxidation-barrier, or combinations thereof. Examples of rareearth oxides in the lower barrier-layer 31 include oxides of scandium,yttrium, lanthanum, cerium, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, and lutetium.

The lower barrier-layer 31 can be distinct from the wires 12, meaning(a) there can be a boundary line or layer between the wires 12 and thelower barrier-layer 31; or (b) there can be some difference of materialof the lower barrier-layer 31 relative to a material of the wires 12.For example, a native aluminum oxide can form at a surface of aluminumwires 12. A layer of aluminum oxide (oxidation-barrier) can then beapplied to the wires. This added layer of aluminum oxide can beimportant, because a thickness and/or density of the native aluminumoxide can be insufficient for protecting a core of the wires 12 (e.g.substantially pure aluminum) from oxidizing. In this example, althoughthe oxidation-barrier (Al₂O₃) has the same material composition as asurface (Al₂O₃) of the wires 12, the oxidation-barrier can still bedistinct due to a boundary layer between the oxidation-barrier and thewires 12, a difference in material properties, such as an increaseddensity of the oxidation-barrier relative to the native aluminum oxide,or both.

Upper Barrier-Layer

As illustrated on WGP 40 in FIG. 4, an upper barrier-layer 41 can belocated at an outermost surface 14 _(UO) of the top protection layer 14_(U), at an outermost surface 14 _(LO) of the bottom protection layer 14_(L), at some or all surfaces of the channels 13, or combinationsthereof. Such surfaces of the channels 13 can include an innermostsurface 14 _(UI) of the top protection layer 14 _(U) adjacent and facingthe channels 13, a surface 14 _(LI) of the bottom protection layer 14_(L) in the channels 13, and a side-wall surface 12 _(s) of the wires inthe channels 13. Having the upper barrier-layer 41 in these locationscan allow it to protect many or all exposed surfaces of the protectionlayer(s) 14. For improved adhesion of the wires 12 to the protectionlayer(s) 14, the upper barrier-layer 41 can be absent or not locatedbetween the proximal end 12 _(p) of each wire 12 and the bottomprotection layer 14 _(L), between the distal end 12 _(d) of each wire 12and the top protection layer 14 _(U), or both.

The upper barrier-layer 41 can be a conformal coating. The upperbarrier-layer 41 can cover a large percent of the covered regions, suchas for example ≥50%, ≥75%, ≥90%, ≥95%, or ≥99% of covered regions (14_(UO), 14 _(LO), surfaces of the channels 13, or combinations thereof).The amount of coverage can depend on conditions of WGP use and onwhether complete coverage is required.

The upper barrier-layer 41 can include various chemicals to protectagainst oxidation, corrosion, or both. Many desirable chemicals for theupper barrier-layer 41 can be destroyed by heat during deposition of thetop protection layer 14 _(U); therefore, it may be desirable to firstapply the top protection layer 14 _(U), then apply the upperbarrier-layer 41. It can be important for providing structural supportto the wires 12 for the top protection layer 14 _(U) to be a continuouslayer. The top protection layer 14 _(U) can be applied in a continuouslayer, with the top protection layer 14 _(U) on each wire 12 touchingthe top protection layer 14 _(U) on adjacent wires, but with a permeablejunction 42 between the top protection layer 14 _(U) on adjacent wires12. This permeable junction 42 can have small spaces to allow chemistryof the upper barrier-layer 41 to enter and coat the surfaces of thechannels 13; but these permeable junctions 42 can be small enough to notadversely affect structural support for the wires 12. The top protectionlayer 14 _(U) can be applied with these characteristics by theprocedures described below in the method of making section.

The upper barrier-layer 41 can include an amino phosphonate, ahydrophobic chemical, a metal oxide such as those described above forthe lower barrier-layer 31, or combinations thereof. The aminophosphonate can be nitrilotri(methylphosphonic acid) with chemicalformula N[CH₂PO(OH)₂]₃, also known as ATMP. Combining both ATMP and thehydrophobic chemical can improve protection of the WGP initially andlong-term. The hydrophobic chemical can provide superior resistance towater initially, but can also break down more quickly under hightemperatures during use of the WGP. The ATMP can be more resistant toheat and thus provide protection for a longer time than the hydrophobicchemical. The ATMP can be a lower layer, sandwiched between thehydrophobic chemical and the wires 12.

The mass fraction of ATMP/hydrophobic chemical can vary depending on thecost of each and whether initial WGP protection or long-term WGPprotection is more critical. For example, this mass fraction can be ≤10,≤5, or ≤2 and ≥1, ≥0.5, or ≥0.1.

Examples of the hydrophobic chemical include a silane chemical, aphosphonate chemical, or both. For example, the silane chemical can havechemical formula (1), chemical formula (2), or combinations thereof, andthe phosphonate chemical can have chemical formula (3):

where r can be a positive integer, each R¹ independently can be ahydrophobic group, each X and Z can be a bond to the wires 12, and eachR³ and R⁵ can be independently any chemical element or group.

Examples of R³ and R⁵ include a reactive-group, R¹, R⁶, or a bond to thewires X or Z. Examples of the reactive-group include —Cl, —OR⁷, —OCOR⁷,—N(R⁷)₂, or —OH. Each R⁷ can independently be —CH₃, —CH₂CH₃, —CH₂CH₂CH₃,any other alkyl group, an aryl group, or combinations thereof.

Examples of R¹ include a carbon chain, a carbon chain with at least onehalogen, a carbon chain with a perfluorinated group, or combinationsthereof. Examples of a length of the carbon chain or of theperfluorinated group of the carbon chain include ≥3 carbon atoms, ≥5carbon atoms, ≥7 carbon atoms, or ≥9 carbon atoms and ≤11 carbon atoms,≤15 carbon atoms, ≤20 carbon atoms, ≤30 carbon atoms, or ≤40 carbonatoms. A carbon atom of the carbon chain can bond directly to the Siatom or to the P atom. R¹ can comprise or consist ofCF₃(CF₂)_(n)(CH₂)_(m), where n≥1, n≥2, n≥3, n≥5, or n≥7 and n≤8, n≤9,n≤10, n≤15, or n≤20; and m≥1, m≥2, or m≥3 and m≥3, m≤4, m≤5, or m≤10.

The lower barrier-layer 31 can be an outermost layer of solid materialas shown in FIG. 3, and can be exposed to air. Alternatively, the upperbarrier-layer 41 can be an outermost layer of solid material and can beexposed to air as shown in FIGS. 4-7. As illustrated in FIGS. 5-6, thelower barrier-layer 31 can be combined with the upper barrier-layer 41.This combination can provide superior protection against oxidation andcorrosion, but also adds cost to the WGP.

The lower barrier-layer 31, the upper barrier-layer 41, or both can be aconformal-coating. Use of a conformal-coating can result in a smallerchemical thickness T₃₁ or T₄₁, thus saving cost and reducing anydetrimental effect of the chemical on WGP performance.

Barrier-Layer Thickness

It can be important to have sufficiently large thickness T₃₁ of thelower barrier-layer 31, sufficient thickness T₄₁ of the upperbarrier-layer 41, or both, in order to provide sufficient protection tothe wires 12. Examples of minimum thicknesses T₃₁ or T₄₁ include ≥0.1nm, ≥0.5 nm, ≥1 nm, ≥5 nm, or ≥10 nm. It can be important to have asmall thickness T₃₁ of the lower barrier-layer 31, a small thickness T₄₁of the upper barrier-layer 41, or both, in order to avoid or minimizedegradation of WGP performance caused by this chemistry. Examples ofmaximum thicknesses T₃₁ or T₄₁ include ≤12 nm, ≤15 nm, ≤20 nm, or ≤50nm. These thickness values can be a minimum thickness or a maximumthickness at any location of the conformal-coating or can be an averagethickness, as specified in the claims.

Absorptive

As illustrated on WGP 60 in FIG. 6, each of the wires 12 can include areflective layer 62 sandwiched between absorptive layers 63. Because theabsorptive layers 63 readily increase in temperature as they absorblight, it can be particularly useful to sandwich the wires 12 of dualabsorptive WGPs between a pair of protection layers 14. For improvedheat transfer, each absorptive layer 63 can adjoin a protection layer14.

The protection layers 14 can be heat sinks for heat absorbed by theabsorptive layers 63. Increased volume of the protection layers 14 canbe beneficial to allow sufficient volume for absorption of this heat.Thus, for example, a volume of each of the protection layers 14 can be≥2 times, ≥3 times, ≥5 times, ≥8 times, ≥12 times, or ≥18 times a volumeof each absorptive layer 63.

Substrate, Single Barrier-Layer, No Barrier-Layer

As further illustrated on WGP 60 in FIG. 6, a substrate 61 can beadjacent to or can adjoin the outermost surface 14 _(LO) of the bottomprotection layer 14 _(L).

The substrate 61 can be made of an optically transparent material forthe wavelength range of use, such as for example ultraviolet, visible,infrared, or combinations thereof. The substrate 61 can have a thicknessTh₆₁ and material for providing structural support for the wires 12 andthe protection layers 14. For example, the thickness th₆₁ can be ≥0.1mm, ≥0.3 mm, ≥0.5 mm, or ≥0.65 mm. The added substrate 61 might not beneeded if the protection layers 14 provide sufficient structural supportfor the wires 12. Performance can be improved and cost reduced by such adesign.

As shown on in FIG. 7, WGP 70 can include an array of wires 12 on asingle protection layer 14. An upper barrier-layer 41, including ahydrophobic chemical, ATMP, or both, as described above, can be aconformal coating on the wires 12 and an exposed surface of thesubstrate 61. WGP 70 can also include the lower barrier-layer 31 betweenthe upper barrier-layer 41 and the wires.

As shown on in FIG. 8, WGP 80 can include an array of wires 12sandwiched between a substrate 61 and a single protection layer 14. WGP80 can be a lower cost WGP.

Optical System

Optical system 90, illustrated in FIG. 9, comprises at least one WGP 94according to a design described herein and a spatial light modulator 92.If two WGPs 94 are used, the spatial light modulator 92 can be locatedbetween them.

If the bottom protection layer 14 _(L) is thicker than the topprotection layer 14 _(U), the top protection layer 14 _(U) can face thespatial light modulator 92 and can be located closer to the spatiallight modulator 92 than the bottom protection layer 14 _(L). Having thethicker protection layer 14 facing away from the spatial light modulator92 can minimize distortion of the light.

Light from a light source 93 can be polarized at the WGP. The spatiallight modulator 92 can be located to receive a transmitted or reflectedlight beam from the WGP 94. The spatial light modulator 92 can have aplurality of pixels, each pixel capable of receiving a signal. Thesignal can be an electronic signal. Depending on whether or not eachpixel receives the signal, or the strength of the signal, the pixel canrotate a polarization of, or transmit or reflect without causing achange in polarization of, a part of the beam of light. The spatiallight modulator 92 can include liquid crystal and can be transmissive,reflective, or transflective.

Light from the spatial light modulator 92 can be polarized at a secondWGP 94, if two WGPs are used. The light can then enter device 91, whichcan be a projection system or color-combining optics, such as forexample an X-Cube.

Method

A method of manufacturing a WGP can comprise some or all of thefollowing steps, which can be performed in the following order or otherorder if so specified. Some of the steps can be performed simultaneouslyunless explicitly noted otherwise in the claims. There may be additionalsteps not described below. These additional steps may be before,between, or after those described. Components of the WGP, and the WGPitself, can have properties as described above.

A step, illustrated in FIG. 10, includes applying film(s) 102 on top ofthe bottom protection layer 14 _(L). For example, the film(s) 102 can besputtered onto the bottom protection layer 14 _(L). The film(s) 102 caninclude reflective layer(s), transparent layer(s), absorptive layer(s),or combinations thereof.

A step, illustrated in FIG. 11, includes etching the film(s) 102 to forman array of wires 12 and channels 13 between adjacent wires 12. A step,illustrated in FIG. 12, includes etching beyond the proximal end 12 _(p)of the wires 12 into the bottom protection layer 14 _(L) for a depthD_(14L), thus increasing the size of the channels 13.

A step, illustrated in FIG. 13, includes applying a lower barrier-layer31.

The lower barrier-layer 31 can be applied to an exposed surface of thewires 12 and a surface 14 _(LI) of the bottom protection layer 14 _(L)in the channels 13. The lower barrier-layer 31 can thus be applied to adistal end 12 _(d) of the wires 12 farthest from the bottom protectionlayer 14 _(L), a side-wall surface 12 _(s) of the wires 12 in thechannels 13, and a surface 14 _(LI) of the bottom protection layer 14_(L) in the channels 13. The lower barrier-layer 31 can be applied by ina conformal layer, such as by atomic layer deposition. The lowerbarrier-layer 31 can thus be a conformal coating, providing a thin layerof protection while retaining the channels 13 air-filled.

A step, illustrated in FIG. 14, includes applying a top protection layer14 _(U). The top protection layer 14 _(U) can be applied, such as forexample as described below, to span the channels and to keep thechannels 13 air filled. The term “air filled” herein means that anair-filled channel remains, but such channel may be reduced in size bythe top protection layer 14 _(U) extending into the channels 13, such asfor example partially along sides 12 _(s) of the wires 12.

Further, by the method described below, the top protection layer 14 _(U)on adjacent wires 12 can touch but retain a permeable junction 42between the top protection layer 14 _(U) on adjacent wires 12. Also, bythe method described below, each channel 13 can extend beyond the distalend 12 _(d) of the wires 12 into the top protection layer 14 _(U) for adepth D_(14U), thus increasing the size of the channels 13 and improvingperformance.

The top protection layer 14 _(U) can be applied by sputter deposition.Following are example deposition conditions in order to achieve theproperties described above. A pressure of the chamber can be 1-5 mTorr.Deposition temperature can be about 50° C. A mixture of O₂ gas and Argas, with a ratio of about 1:1, can blow through the chamber. Depositioncan be performed with a bias voltage of about 1000 volts and power of4000 watts. The wires can have a pitch P of about 100-140 nm, wire widthW₁₂ of about 30-40 nm, wire thickness T₁₂ of about 250-300 nm.Deposition conditions can be adjusted to shape the top protection layer14 _(U). For example, bias voltage, gas flow rate, gas ratio, andchamber pressure can be adjusted to change the rate of deposition of thetop protection layer 14 _(U), and thus change its shape. Theaforementioned conditions can vary depending on the sputter tool used,the type of target material, the type of sputter deposition, and desiredshape of the top protection layer 14 _(U).

A step, illustrated in FIG. 15, includes applying an upper barrier-layer41. The upper barrier-layer 41 can be applied by various methods,including chemical vapor deposition. The upper barrier-layer 41 can belocated at an outermost surface 14 _(UO) of the top protection layer 14_(U), at an outermost surface 14 _(LO) of the bottom protection layer 14_(L), at some or all surfaces of the channels 13, or combinationsthereof. Locations where coverage is not desired can be blocked duringdeposition.

The upper barrier-layer 41 can enter and coat the channels 13 byentering through the permeable junctions 42 in the top protection layer14 _(U) between adjacent wires 12. Deposition conditions can be adjustedto allow or improve entrance of the upper barrier-layer 41 through thepermeable junctions 42 into the channels 13. For example, the chemistryof the upper barrier-layer 41, in liquid phase, can be poured into aflask. This liquid can be pumped or drawn into a container attached toan oven containing the WGP. The oven can have a pressure and temperaturefor the chemistry to flash to vapor. For example, the oven can have atemperature of ≥100° C. and ≤200° C. and a pressure of ≥1 Torr and ≤3Torr.

Chemistry used to apply the top protection layer 41 can includeSi(R¹)_(i)(R³)_(j). i can be 1 or 2. j can be 1, 2, or 3. i+j can equal4. R³ and R¹ are described above. The Si(R¹)_(i)(R²)_(j) can be in agaseous phase in the oven, then vapor deposited onto the WGP.

What is claimed is:
 1. A method of manufacturing a wire grid polarizer(WGP), comprising: providing an array of wires on a bottom protectionlayer with channels between adjacent wires, the channels being airfilled; applying an amino phosphonate as a conformal coating on thewires and on the bottom protection layer in the channels; and applying ahydrophobic chemical as a conformal coating on top of the aminophosphonate.
 2. The method of claim 1, wherein: applying the aminophosphonate includes applying the amino phosphonate by liquid immersiondeposition; applying the hydrophobic chemical includes applying thehydrophobic chemical by vapor deposition; and the hydrophobic chemicalis an outermost solid material.
 3. The method of claim 1, wherein anorder of steps in the method is providing the array of wires, applyingthe amino phosphonate, then applying the hydrophobic chemical.
 4. Themethod of claim 1, wherein the amino phosphonate has chemical formulaN[CH₂PO(OH)₂]₃, and the amino phosphonate is sandwiched between thehydrophobic chemical and the wires.
 5. The method of claim 1, whereinthe amino phosphonate has chemical formula N[CH₂PO(OH)₂]₃, and a massfraction of amino phosphonate/hydrophobic chemical is ≥0.5 and ≤5. 6.The method of claim 1, wherein the hydrophobic chemical includesSi(R¹)_(i)(R³)_(j), where i is 1 or 2, j is 1, 2, or 3, i+j=4, each R¹independently is a hydrophobic group including CF₃(CF₂)₃(CH₂)_(m), m≥1and m≤10, and each R³ independently is any chemical element or group. 7.The method of claim 6, wherein each R³ independently is —Cl, —OR⁷,—OCOR⁷, —N(R⁷)₂, or —OH; and each R⁷ independently is —CH₃ or —CH₂CH₃.8. The method of claim 6, wherein m≤3.
 9. The method of claim 6, whereinm=2.
 10. The method of claim 1, wherein the hydrophobic chemicalincludes Si(R¹)_(i)(R³)_(j), where i is 1 or 2, j is 1, 2, or 3, i+j=4,each R¹ independently is a hydrophobic group includingCF₃(CF₂)₂(CH₂)_(m), m≥1 and m≤10, and each R³ independently is anychemical element or group.
 11. The method of claim 10, wherein m≤3. 12.The method of claim 1, further comprising applying a top protectionlayer after providing the array of wires and before applying the aminophosphonate and the hydrophobic chemical, wherein: the array of wires issandwiched between the top protection layer and the bottom protectionlayer, the top protection layer spanning the channels, keeping thechannels air filled, the bottom protection layer and the top protectionlayer each have a melting temperature ≥600° C. and water solubility≤0.005 g/L; thickness of the top protection layer is ≥10 nm and ≤1 μm;and thickness of the bottom protection layer is ≥300 μm and ≤5 mm; thetop protection layer is applied to allow each channel to extend beyond adistal end of the wires, farthest from the bottom protection layer, intothe top protection layer for a depth ≥10 nm.
 13. The method of claim 12,wherein the bottom protection layer and the top protection layer eachhave a coefficient of thermal conductivity ≥2 W/(m*K); and an oxygendiffusion coefficient ≥10⁻²¹ m²/s.
 14. The method of claim 12, whereinthe bottom protection layer and the top protection layer each haverefractive index 1.3≤n≤1.8 and extinction coefficient ≤0.1 across thevisible light spectrum.
 15. A method of manufacturing a wire gridpolarizer (WGP), comprising: providing an array of wires on a bottomprotection layer with channels between adjacent wires, the channelsbeing air filled; and applying a hydrophobic chemical as a conformalcoating on top of the wires, the hydrophobic chemical includingSi(R¹)_(i)(R³)_(j), where i is 1 or 2, j is 1, 2, or 3, i+j=4, each R¹independently is a hydrophobic group including CF₃(CF₂)₃(CH₂)_(m), m≥1and m≤10, and each R³ independently is any chemical element or group 16.The method of claim 16, wherein m≤3.
 17. The method of claim 16, whereineach R³ independently is —Cl, —OR⁷, —OCOR⁷, —N(R⁷)₂, or —OH; and each R⁷independently is —CH₃ or —CH₂CH₃.
 18. The method of claim 16, whereinm=2.
 19. A wire grid polarizer (WGP), comprising: an array of wires on abottom protection layer with channels between adjacent wires, thechannels being air filled; a hydrophobic chemical as a conformal coatingon top of the wires, the hydrophobic chemical including chemical formula(1), chemical formula (2), or combinations thereof:

where r is a positive integer, each R¹ is CF₃(CF₂)₃(CH₂)_(m), where m≥1and m ≤10, X is a bond to the wires, and each R³ independently is anychemical element or group.
 20. The method of claim 19, wherein each R³independently is —Cl, —OR⁷, —OCOR⁷, —N(R⁷)₂, or —OH; and each R⁷independently is —CH₃ or —CH₂CH₃.